Method of effecting chemical conversions



April v13, 1954 P. c. KEITH METHOD-0F EFFECTING CHEMICAL coNvERsIoNs Filed Aug. 16. 1949 CT GAS) PRODU IIFIIII@ I6 PERcIv/II. c. KEITH MVVNTOR [am ATTORNIEY Patented Apr. 13, 1954 METHOD oF EFFECTING CHEMICAL coNvEasioNs Percival C. Keith, Peapack, N. J., assignor to The M. W. Kellogg Co., Jersey City, N. J., a corporation of Delaware Continuation of application Serial No. 684,684, July 19, 1946. This application August 16, 1949,

Serial No. 110,541

6 Claims.

The present invention relates to improvements in process, and apparatus, for effecting chemical conversion reactions, particularly, those conversion reactions vrequiring for their satisfactory practice the supplying of and/or withdrawing heat to or from a gaseous reactant in a very short period of time.

This application is a continuation of my application Serial No. 684,684, led July 19, 1946, which in'itself is a continuation-in-part of my application S. N. 429,266, iiled February 2, 1942. Heretofore, certain conversion reactions have been known and practiced on a very small scale and with laboratory equipment, but since they were. not amenable to satisfactory practice on large scale apparatus and under commercial conditions, have 'remained merely of academic interest.` This type of conversion reaction, in general, consists of those requiring that a gaseous reactant or reactants be brought up to an elevated temperature in a very short period of time and, in many instances, likewise maintained at this temperature for a very short period. The provision of a methcd and apparatus whereby such conversion reactions may be carried out with satisfactory yields of the desired products on a large commercially feasible scale, and with commercially available apparatus, constitutes a primary object of my invention.

A further object of my invention is the provision oi method and apparatus whereby endothermic chemical conversion reactions requiring the maintenance of a reactant, or reactants, at specified temperatures for an extremely short period of time may be satisfactorily accomplished and which are not subject to the limitations en tailedby the supplying of the necessary heat largely'orentirely by means cf indirect heat exchange.

Pursuant to the present invention a stream of the gaseous reactant` is mixed with heated particles of a solid-contact material, the particles thus addedserving as a heat carrier and being at a temperature and in suicient amount to substantially instantaneously heat the gaseous reactant to and maintaining it at the required `con version temperature.

A further feature of the process comprises quickly cooling the stream of conversion products to a temperature level at which undesired reactions are precluded, by passing them to a suitable cooling or quenching zone, this zone preferably comprising a cooled psuedo-liquid mass of 4v,the particles of contact material, Various other features, advantages and objects of my invention will be apparent from the following detailed description thereof given in con-n nection with the appended drawing.

The appended drawing illustrates diagrammatically a suitable arrangement of apparatus, and process iiow, for the practice of the inven tion pursuant to one illustrative embodiment. As shown therein, the process may suitably involve three primary units or zones, comprising a powder heating zone wherein the particles of solid contact material are preheated to a suitn able temperature, a conversion or reaction zone wherein the solid particles are suspended in and contacted with a stream of the gaseous reactant for the requisite short period of time, and a cooling or quenching zone wherein the temperature of the conversion products is rapidly lowered to a desired level.

The particles of solid contact material may be preheated to the required temperature for inroduction into the reaction zone by any one of various available heating methods such as by heating in a rotary kiln, or the like. However, a preferred procedure as shown in the drawing consists in heating these particles under conditions wherein they constitute a pseudo-liquid or fluidized bed, hereafter referred to as dense phase zone. This particular condition in general is characterized by the relatively high concentration of the particles of solid contact agent measured in terms of the quantity thereof per unit volume of occupied space, and by the maintained low velocity flow of heating gas upwardly through the zone. The maintenance of a. definite minimum gaseous velocity is regarded as de-V sirable to maintain the bed in a turbulent iiuidized state. Preferably, the upward velocity ci the gas through the heating zone is sufficiently high to maintain the dense phase of solid parti-1 cles in a turbulent condition wherebythe individual particles are caused to circulate throughout the dense phase zone. This turbulent and circulatory motion of the solid particles results in the maintenance of a substantially uniform temperature throughout the dense phase. The optimum velocity both with respect to its minimum and maximum value will be dependent upon the density, size and shape of the solid particles employed and the density and viscosity of the heating gas, so that tor any particular size or Sizes of particles and quality of heating gas this velocity is adjusted within a range so as to maintain the desired turbulent dense phase corn dition. For example, employing a powdered contact material consisting or a range of mixed size Vrelative heights of the individual cones.

particles, all or most of which are smaller than 100 microns, and operating at atmospheric pressure with gases consisting essentially of air ad.- mixed with combustion products, a gas velocity within the range of 1.5 to 2 it. per second is re* garded as suitable.

Powdered solid material of'this character in its ordinary non-aerated state will exhibit a definite angle of repose characteristic of a nely divided solid. For example, a powdered material of given physical characteristics when poured on to a horizontal supporting surface in such manner as to form cones of the powder will produce cones of equivalent inclinations to the horizontal, that is equal angles of repose regardless of the Accordingly, a definite angle of repose on pouring into an unconfined space is Van inherent characteristic of non-aerated finely divided powdered solids. Due to their high specific surface powdered solids may be aerated in such a manner that a film of the aerating fluid is produced on the surface thereof with the result that the individual particles will flow readily with respect to the adjacent particles, and accordingly, these particles behave in the same characteristic manner as the particles constituting a liquid. For example, these aerated particles no longer exhibit a definite angle of repose and 'flow similarly to a liquid.

The solid particles in this aerated condition may, therefore, be described as being pseudo-liquid or as being inthe form of a solid-emulsion, one component or phase of which is made up of the solid particles and the second component or continuous phase consisting of the air or other gaseous films.

The dense pseudo-liquid phase of the particles of solid contact material (zone A) extends only partially through the powder heating zone or heater I, an approximate upper horizontal level thereof being indicated by dotted line 2. The space (zone B) in the reactor above this level constitutes a solid-vapor disengaging space, accordingly only a relatively small proportion of the total quantity of contact material introduced through lines 3 and 4 is carried out overhead with the heating gases leaving zone B through gas outlet line 5. Heated contact material preferably is withdrawn from the heating zone by a withdrawal passageway 'I opening directly into the dense phase zone A. Y

Particles of solid contact material may be sup- 3 leading to the base of the powder heater I. Solids-pump In may be of a suitable design to introduce the powdered material under an opposing fluid pressure, for example, a solids-pump of the Fuller Kinyon. type such as described in Kinyon Patent 1,553,539. During normal operau tion the main amount of contact material circulated is derived by recycling from subsequent portions of the system, and only make up material, to compensate for unavoidable losses or the like, is supplied from hopper 9.

Recirculated or recycled particles of contact material are introduced to inlet lines 3 and 4, respectively, from discharge line l I of the primary separator I 2, and discharge line I3 from the base of the cooler or quencher I4. A suitable conveying gas is supplied to the inlets of lines 3 and 4 through lines I5 and I E and the conveying medium thus supplied may suitably be a portion or all of the heating gas utilized in zone I to heat the contact material to Vthe required temperature.

For example, Va fuel gas may be supplied through 7' line I5 and an oxygen-containing gas such as air supplied through line I6. The suspensions of the particles of contact material and conveying medium are carried through lines 3 and 4 to the conical base I1 which servesl as a distributor for zone I, the lower boundary of the dense phase zone A being approximately defined by the upper boundary of the cone I'I as indicated by dotted line I8. When required, additional combustible gas and/ or air may be introduced into distributing cone I 'I from inlets therein, not shownor at any other desired points throughout the length of the dense phase zone. The cross sectional area of zone I is so proportioned with respect to the quantity of gas introduced that the upward velocity o the gas therethrough is relatively low and adapted to provide the dense pseudo-liquid phase hereinbefore described.

' The temperature of the solid particles recycled through lines 3 and 4 usually will be suicient to start combustion of the combustible gas in zone A. Zone A serves not only as a heating zone but also as a zone for removal of any undesirable constituents such as carbonaceous material deposited on the contact material during conversion, and' also utilizesv such deposits as fuel in the heating operation.

Fluo gas is withdrawn overhead from the gassolids disengaging space B through line 5 and passed to a suitable separating system such'as a cyclone separator or separators I9 wherein suspended solids are separated and returned to the system, suitably through lineY 20 leading back to the dense phase zone A. The hot flue gas discharged from separator I9 is suitably passed through a heat exchanger or waste heat boiler 2l'.

for the recovery of' its heat: content and is then discharged from the system, eithery through pires-k sure control equipment or vacuum pumps (not shown) depending on the desirability of operating zone I at pressures above or below atmospheric pressure. Heated particles of solids contact material are withdrawn from the` dense phase zone A through an outlet pipe I opening directly into this phase. In certain instances a stripping and aerating gas may be introduced into pipe 'l through lines23 for the purpose of displacing any gases entrained therewith which would be undesirable in the subsequent reaction, and maintaining the withdrawn material in standpipes 24 in a flowable pseudo'- liquid condition. From outlet l, the hot particles of contact material are passed to the reaction zone through standpipe line 24 at a rate controlled by valve 2,5. The pressure at valve 25 is approximately the sum of the pressure at 43, the fluid pressure in zoneB, the static head of zone A and the static head of uidized particles in the outlet standpipe 24. The height of standpipe 24 may be suitably dimensioned to provide any desired pressure at its discharge opening and hence its height willibc varied depending upon the back pressure upc this opening from the reaction zone. A suitable feed is supplied `to the system through line 26 and is preferably preheated,in heating coil 21 to a temperature approximating but below that at which undesired reactions would occur. l duced into the reaction or conversion zone through line 28.

In the initial part of the reaction zone, the vaporized feed or gaseous reactant mixes with the stream of hot particles of contact material introduced through line 24, andthe gaseous suspension thus produced is carried at a high velocity The preheated feed is then intro-V through the reaction zone consisting of chamber 29 and the upper section of primary separator I2. The temperature of the material introduced through line 24 and the quantity thereof is such as to heat the gaseous reactant (or reactants) to and maintain it substantially at the required reaction temperature during the passage of the reactant and suspended particles through the reaction zone. Due to the rapid intimate contact between the particles and the gaseous reactant, and the large amount of heat exchangevsurface thus made available, the temperature of the gaseous reactant is raised to the required reaction temperature substantially instantaneously and undesirable reactions occurring at intervening temperatures are thereby reduced to a minimum.

VFrom reaction zone 2s the suspension is preferably passed to a suitable separator adapted to separate a portion `of the suspended solids at a high velocity and consequent relatively short interval of time, for example, a gas-solids separator I2 of the cyclone type. The gas space in separator I2, which operates at reaction temperature, conm stitutes-a part of the total reaction zone. Solids separated in separator I2 are withdrawn from its bottom hopper through line I I, and returned through line 4 to zone I. products and remaining suspended solids particles are withdrawn from the top of the separator through line 3lland passed to a cooling or quenching zone I4. i

`The length of the conversion chamber and the dimensions of the primary separator are so selected that the time required for the gaseous reactant to pass therethrough is of the required short duration. The specific purpose `of primary `separator I2 is torecycle at the highest possible temperature a large quantity of the solid particles for the sake of heat economy. Of necessity, this type of apparatus which operates substan tially at the reaction temperature, provides addin tional reaction time to the time provided in the reaction zone. In the case of certain reactions which may advantageously be carried out by the process herein disclosed, the maximum allowable reaction time is of such short duration that it precludes the use of a primary separator. In these cases I prefer to operate without the primary separator i2, that is, the efflux from the reaction. zone flows directly into line Sil. On the other hand certain other reactions are encountered requiring that the gaseous reactant be maintained at an elevated temperature over a fairly long period of time. ln such cases the process may be advantageously modified by utilizing an arrangement similar to that shown except that primary separator i2 may be constructed to contain a fluidized bed maintained at substantially reaction temperature.

Various means may be provided for quickly cooling the conversion products discharged through line 3i] to a temperature level at whichundesirable reactions are inhibited, such as a liquid quenching bath, liquid spray, or the like. However, an arrangement greatly preferred is that shown wherein the cooling zone comprises a `body of the` particles of contact material in a turbulent iiuidized or pseudo-liquid condition similar to the preferred condition maintained in the powder heating Zone l, and governed by the same factors but4 maintained at the lower temperature to which the `reaction products must be rapidly cooled. In order to provide this conditionA cooler -I4 is made of a suitable crosssectional area such that the gaseous conversion productsl Gaseous conversion discharged thereto through line '30 travel upwardly through the cooler at a relatively low velocity adapted to provide the desired turbulent pseudo-liquid phase. A perforated plate or other` suitable means .3i may be provided at the upper portion of the distributing cone 32 to insure an even `distribution of the gas introduced through line Sil. Zones A and B in cooling zone It cor- A respond to zones A and B in heating zone l. The

pseudo-liquid phase A' may be cooled by any suitable means such as cooling coils disposed directly therein. A preferred method for cooling Zone A', as shown, consists in withdrawing solid particles therefrom and recycling these through an external cooling zone and then back to zone A through the circuit constituted by elements 3.3, 35, 3E and 3l. Due to the highly turbulent movement of the solid particles maintained in zone A the cooled particles thus recycled are quickly distributed throughout zone A' and a substantially uniform low temperature is thereby maintained.

From zone It, gaseous conversion products and residual suspended solid particles are withdrawn overhead and passed to a suitable separating system such as a low velocity settler, orI optionally a cyclone separator or separators 34 wherein substantially complete separation of the suspended solids is effected. The gaseous conversion prod-v ucts are forwarded through line liz to a suitable conventional products recovery means or system, such as an absorber, or the like. The pressure in line 42 may be maintained above or below atmospheric pressure by suitable equipment as in the case of line 43.

The solids Withdrawn from separator 34 may suitably constitute those recycled through the external cooling zone 31 for the purpose of temperature control in zone I4. These particles are preferably suspended in. a portion of the product gas by-passed through line 36 by compressor 4! and returned to the dense phase zone A1 by way of line` 35 and through the cooler or heat exchanger 3l'.

All the solid particles in suspension in the gas passing through line 3l) are eventually recirculated to the powder heating zone by withdrawing them through outlet 4U and discharge line I3. ILine I3, and also line I I, may be standpipes similar to pipe 2.4 and also are preferably supplied with means similar to line 23 for supplying an aerating and/or stripping uid. Preferably as large a fraction of solid particles is separated in separator I2 as possible, as the latter particles are at substantially higher temperature level than those withdrawn through line I3, but, as stated above, the limitations of maximum length of reaction time impose limitations on the use of primary separator i2.

The particles of solid contact material utilized are preferably of a refractory character adapted to be subjected to the elevated temperatures involved without being fused. In general, the various materials utilized in the production of high temperature refractories, such as Carborundrum, re brick, magnesia, silica, bauxite, pumice, plumbago graphite, and the like, constitute suitable base materials for this purpose.

Catalytic material of refractory character may be used. The contact material is preferably employed in nely divided or powdered condition in order to provide a high specific surface and consequent large amount of Vheat exchange surface. For example, the contact material utilized may consist largely or entirely of particles of' 100 microns or smaller in average diameter. While the material utilized may suitably be catalytic with respect to the particular reaction involved, the process contemplates reactions wherein the contact material employed is noncatalytic and serves primarily as a heat carrier.

it will be apparent to those skilled in the art that such factors entering into the process as, (l) a temperature and quantity of the contact material introduced into the conversion zone, (2) the temperature of the conversion zone, (3) the time of contact in the conversion zone and consequent dimensions of the conversion zone, and (4) temperature of the cooling zone, will be dependent upon the particular reaction involved and the intermediate conversion product desired. Accordingly, these factors in any given instance are selected and regulated in accordance withV the particular reaction involved and the products desired. The practice of the process, however, may be further exemplified by the following example of operating conditions suitable I`or the production of acetylene pursuant to the endothermic reaction represented by the following equation:

Qucnchlng zone S Under the above conditions acetylene may be producedV up to yields of approximately 5() per cent.

it is to be understood that the above example and conditions are merely illustrative and that the process may be applied to a wide variety of reactions requiring that a gaseous reactant be heated to an elevated temperature in a very short space of time and maintained at such a temperature for a very short space of time, for examplea fraction of a second as above exemplieol. Y

I claim:

l. Themethod of conducting an endothermic chemical reaction in the presence oi' a solid catalyst in powdered condition at a high temperature with a short contact time between reaction material and catalyst which comprises establishing Van elevated reservoir of hot powdered catalyst, establishing a reaction zone at a substantially lower level, establishing a column of hot powdered catalyst in iluidized condition betweensaid reservoir and said reaction zone, pron viding for a continuous open ow of catalyst from the bottom of said column into said reaction zone, admiring with catalyst leaving said column a gaseous reactant, causing said gasecus reactant to flow at a suiciently high velocity to carry said hot powdered catalyst through said reaction zone concurrently with said reactant and at substantially the same velocity to where the catalyst with gaseous products of reaction are discharged from the reaction zone at its outlet, said velocity being preselected to provide the desired short contact time between catalyst and reactant, abruptly separating said powdered catalyst from gaseous products of reaction at the outlet of .said rea ction zone, quenching the products of reaction at the point of separation thereof fromV said catalyst and controlling the temperature of said reaction zone by controlling the temperature and the static head of said luidized solids flowing from the bottom of said column into said reaction zone.

2. The method of conducting an endotherrnic4 chemical reaction in the presence of a solid catalyst in powdered condition at a high temperature with a short contact time between reaction material and catalyst which comprises establishing an elevated reservoir of hot powdered catalyst, establishing a reaction zone at a substantiallyrlower level, establishing a column of hot powdered catalyst in luidized condition between said reservoir and said reaction zone, providing for a continuous open flow of catalyst from the bottom or said column into said reaction zone, admixing with catalyst leaving said column a gaseous reactant, causing said gas-A cous reactant to flow at a sufliciently high velocity to carry said hot powdered catalyst through said reaction zone concurrently with said reactant and at substantially the same velocity to where the catalyst with gaseous products of the reaction are discharged from the reaction zone at its outlet; said velocity and the length of said reaction zone being preselected to' provide the desired short contact time between catalyst and reactant, abruptly separating said powdered catalyst from gaseous products of re` action at the outlet of said reaction zone, owing said gaseous products upwardly into a dense iuidized bedy of catalyst at a temperature adapted to quench said reaction without con-Y densing said gaseous products and controlling the temperature of said reaction zone by controlling the temperature and the ow of said iiuidized solids from the bottom of said column into said reaction Zone.

3. The method of conducting an endotherrnic chemical reaction in the presence of a solid catalyst in powdered condition at a high temperature with a short contact time between reaction material and catalyst which comprises establishing an elevated reservoir of hot powdered catalyst, establishing a reaction zone at a substantially lower level, establishing a column of hot powdered catalyst in iluidized condition between said reservoir and said reaction zone, providing for a continuous open flow of catalyst from the bottom of said column into said reaction zone, admixing with catalyst leaving said column a gaseous reactant, causing said gaseous reactant to iiow at a suiiiciently high velocity to carry said hot powdered catalyst through said reaction Zone concurrently with said reactant and at substantially the same velocity to where the catalyst with gaseous products of the reaction are discharged from the reaction zone at its outlet, said velocity and the length of said reaction zone being preselected to provide the desired short contact time between catalyst and reactant, thereafter passing said catalyst Yand said gaseous products into the bottom portion of an enlarged zone to reduce the velocity of the gases passing upwardly through said enlarged Zone sufficiently to cause the bulli of said catalyst to segregate into aV relatively dense, iluidized layer in the bottom portion cisaid enlarged zone, maintaining said layer within said enlarged zone at a temperature materially below the desired reaction temperature to rapidly cool said reaction products and prevent secondary reactions, and controlling the temperature in said reaction zone by controlling the temperature and the ilow of said Iiuidized solids from the bottom of said column into said reaction zone.

4. A method as described in claim 3 in which the volume cf said iluidized mass of catalyst at quenching temperature is maintained in iluidized condition at least in part by the passage of reaction products upwardly therethrough and a portion of said fluidized particles are continuously withdrawn, cooled to a temperature below that of said reaction products, and reintroduced into said luidized mass of catalyst, and the volurne of said quenching mass is maintained relatively large in relation to the volume of reaction products passed into said mass for quenching.

5. A method as described in claim 4 in which said reaction products leave the reaction zone at temperatures above 2000 F. and said uidized quenching mass is maintained at a temperature below 2000 F., and the volume of said quenching mass is maintained relatively large in relation to the volume of reaction products to cool said reaction products to a temperature below 2000 F.

6. The method of conducting an endothermic chemical reaction in the presence of a solid catalyst in powdered condition at a high temperature with a short contact time between reaction material and catalyst which comprises establishing an elevated reservoir of hot powdered catalyst, establishing a reaction zone at a substantially lower level, establishing a column of hot powdered catalyst in udized condition between said reservoir and said reaction zone providing for a continuous open ilow of catalyst from the bottom of said column into said reaction zone, admixing with catalyst leaving said column a gaseous reactant, causing said gaseous reactant to ow at a suiiciently high velocity to carry said hot powdered catalyst through said reaction zone concurrently with said reactant and at substantially the same velocity to Where the catalyst with gaseous products of reaction are discharged from the reaction zone at its outlet, said Velocity being preselected to provide the desired short contact time between catalyst and reactant, abruptly separating said powdered catalyst from gaseous products of reaction at the outlet of said reaction zone. quenching the products of reaction at the point of separation thereof from said catalyst and controlling the temperature of said reaction zone by controlling the temperature and the flow of said hot powdered catalyst owing Vfrom the bottom of said column into said reaction Zone.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 1,773,611 Banck Aug. 30, 1930 2,303,047 Hemminger Nov. 24, 1942 2,325,516 Holt et a1 July 27, 1943 2,376,190 Roetheli et al May 15, 1945 2,396,109 Martin Mar. 5, 1946 2,437,334. Roetheli Mar. 9, 1948 

1. THE METHOD OF CONDUCTING AN ENDOTHERMIC CHEMICAL REACTION IN THE PRESENCE OF A SOLID CATALYST IN POWDERED CONDITION AT A HIGH TEMPERATURE WITH A SHORT CONTACT TIME BETWEEN REACTION MATERIAL AND CATALYST WHICH COMPRISES ESTABLISHING AN ELEVATED RESERVIOR OF HOT POWDERED CATALYST, ESTABLISHING A REACTION ZONE AT A SUBSTANTIALLY LOWER LEVEL, ESTABLISHING A COLUMN OF HOT POWDERED CATALYST IN FLUIDIZED CONDITION BETWEEN SAID RESERVIOR AND SAID REACTION ZONE, PROVIDING FOR A CONTINUOUS OPEN FLOW OF CATALYST FROM THE BOTTOM OF SAID COLUMN INTO SAID REACTION ZONE, ADMIXING WITH CATALYST LEAVING SAID COLUMN A GASEOUS REACTANT, CAUSING SAID GASEOUS REACTANT, TO FLOW AT A SUFFICIENTLY HIGH VELOCITY TO CARRY SAID HOT POWDERED CATALYST THROUGH SAID REACTION ZONE CONCURRENTLY WITH SAID REACTANT AND AT SUBSTANTIALLY THE SAME VELOCITY TO WHERE THE CATALYST WITH GASEOUS PRODUCTS OF REACTION ARE DISCHARGED FROM THE REACTION ZONE AT ITS OUTLET, SAID VELOCITY BEING PRESELECTED TO PROVIDE THE DESIRED SHORT CONTACT TIME BETWEEN CATALYST AND REACTANT, ABRUPTLY SEPARATING SAID POWDERED CATALYST FROM GASEOUS PRODUCTS OF REACTION AT THE OUTLET OF SAID REATION ZONE, QUENCHING THE PRODUCTS OF REACTION AT THE POINT OF SEPARATION THEREOF FROM SAID CATALYST AND CONTROLLING THE TEMPERATURE OF SAID REACTION ZONE BY CONTROLLING THE TEMPERATURE AND THE STATIC HEAD OF SAID FLUIDIZED SOLIDS FLOWING FROM THE BOTTOM OF SAID COLUMN INTO SAID REACTION ZONE. 